Computational and Theoretical Chemistry最新文献

{"title":"Evaluating the drug delivery and sensing performance of XB23N24, (X = B, Al, Ga) nanocages for gemcitabine anticancer drug","authors":"Natarajan Sathiyamoorthy Venkataramanan","doi":"10.1016/j.comptc.2025.115222","DOIUrl":"10.1016/j.comptc.2025.115222","url":null,"abstract":"<div><div>The interaction of pristine B₂₄N₂₄ nanocages and their Al and Ga-doped nanocages with gemcitabine (GEM) drug was evaluated using density functional theory (DFT) to evaluate BN nanocages for the purpose of GEM nanosensors and drug delivery vehicles. GEM undergoes adsorption on the nanocages either on the boron atom or on the dopant atom. The domain-based local pair natural orbital (DLPNO)-based coupled-cluster method with single, double, and triple excitations (CCSD(T)) based calculations show that the adsorption energy of the drug was −31.79, −61.51, and − 59.60 kcal mol⁻¹ for bare B₂₄N₂₄ and Al and Ga doped nanocages. The doping of metals has enhanced the dipole moment, and the complexes were found to have higher solvation energy than gemcitabine, which helps to improve the solubility and bioavailability of GEM. The highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) and HOMO-LUMO energy gap were sensitive to the dopant atom, and the low energy gap was found for the GEM/B₂₄N₂₄ complex with a substantial increase in electrical conductivity. Noncovalent interaction analysis shows that the hydrogen atom of the amide group in GEM makes a bond with the nanocage, which would reduce the deamination of the group and thereby increase the half-life of the drug. Calculations indicate that the half-life of the drug can be modulated using the judicious choice of attempted frequency and dopant metal atom. The UV–visible spectra of GaB₂₃N₂₄ nanocage were found to show substantial redshift when GEM is adsorbed on it and could, therefore, be a photosensor. The surge of work function upon the adsorption of GEM on B₂₄N₂₄ supports the pristine nanocage, which could be a work function (Φ) type electronic sensor used to detect GEM. Thus, B₂₄N₂₄ nanocages are promising devices for work function-type electronic sensors and Ga-doped nanocages as photosensors and drug carriers.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115222"},"PeriodicalIF":3.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143777019","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the influence of end capped acceptor modification on photovoltaic properties of 1,4-dihydropyridine based functionalized materials: DFT/TD-DFT study","authors":"Iqra Shafiq ,&nbsp;Noor Fatima ,&nbsp;Muhammad Arshad ,&nbsp;Ayesha Tariq ,&nbsp;Laiba Amir ,&nbsp;Saifullah Bullo ,&nbsp;Khalid Abdullah Alrashidi","doi":"10.1016/j.comptc.2025.115218","DOIUrl":"10.1016/j.comptc.2025.115218","url":null,"abstract":"<div><div>A series of organic chromophores (<strong>ITPD1–ITPD6</strong>) <em>via</em> 1,4-dihydropyridine core was designed for organic solar cells (OSC) by modifying the terminal end-capped acceptor units. Quantum chemical investigations were conducted at the M06/6-311G(d,p) functional to collect significant insights about their electronic, structural, chemical, and photonic properties. These findings disclosed that all designed molecules exhibited lower band gaps (2.481–2.765 <em>eV</em>), with redshift spectra (574.92–644.97 <em>nm</em>) as compared to <strong>ITPR</strong> (2.827 <em>eV</em> and 561.47 <em>nm</em>) due to the extended conjugation and strong electron-withdrawing nature of acceptor groups. The open circuit voltage (<em>V</em>_<em>oc</em>) of all studied molecules was computed using donor polymer PBDB-T. Among all, <strong>ITPD4</strong> possesses the smallest band gap (2.481 <em>eV</em>), red-shifted <em>λ</em>_<em>max</em> (644.974 <em>nm</em>) and lowest <em>V</em>_<em>oc</em> (1.425 <em>V</em>) value due to the incorporation of highly electronegative –NO₂ unit. Hence, all these insights uncover the potential of designed molecules for photovoltaic applications.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115218"},"PeriodicalIF":3.0,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular dynamics simulations of irradiation on microstructural and mechanical properties of 1,3,5-trinitro-1,3,5-triazacyclohexane","authors":"Xiyao Yun ,&nbsp;Tao Wang ,&nbsp;Weiyi Li ,&nbsp;Jintao Wang ,&nbsp;Wanxiao Guo","doi":"10.1016/j.comptc.2025.115219","DOIUrl":"10.1016/j.comptc.2025.115219","url":null,"abstract":"<div><div>Energetic materials are utilized in diverse conditions, including environments subject to neutron irradiation. Understanding the effects of irradiation on the microstructures and mechanical properties of energetic materials is crucial for their application in radiation-exposed settings. In this research, we have performed molecular dynamics (MD) simulations to study the irradiation effect on decomposition products, microstructures, and mechanical properties of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX). The results showed that the irradiation damage to RDX primarily manifests in breaking chemical bonds, generating molecular fragments, and forming defects within the crystal. Specifically, as primary knock-on atom (PKA) energy increases, the number of broken chemical bonds shows an upward trend. Following a collision cascade, the primary products induced by irradiation were C₃H₆O₅N₆, NO₂, NO, H₂O, O₂, ·O, and ·OH radicals. An increase in the energy of the PKA was observed to enhance both the decomposition ratio of RDX and the total number of generated species. Furthermore, collision cascades significantly impact the mechanical properties of RDX, leading to a gradual decrease in both young's and shear modulus as decomposition progresses. This results in a reduction of hardness and stiffness, while the rise in Poisson's ratio, Cauchy pressure, and the B/G ratio suggests enhanced ductility. These findings provide a reference for understanding the microstructural damage and mechanical property changes of RDX induced by irradiation</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115219"},"PeriodicalIF":3.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretically probing the asymmetric effect of donor for all-small-molecule organic solar cells","authors":"You-Liang Li ,&nbsp;Jin-Hong Han ,&nbsp;Ying Sun ,&nbsp;Zhi-Wen Zhao ,&nbsp;Qing-Qing Pan ,&nbsp;Xing-Man Liu ,&nbsp;Zhong-Min Su","doi":"10.1016/j.comptc.2025.115214","DOIUrl":"10.1016/j.comptc.2025.115214","url":null,"abstract":"<div><div>The utilization of asymmetric donors is promising in All-Small-Molecule (ASM) organic solar cells (OSCs). In order to analyze the reason for the difference in performance between symmetric and asymmetric systems, the properties of three donors with different end-group units, frontier molecular orbitals (FMOs), dipole moment, reorganization energies in electron transition process, interfacial charge transfer (CT) mechanisms, charge separation rate (<em>k</em>_CS) and charge recombination rate (<em>k</em>_CR) were theoretically studied. Compared to symmetric <strong>SMD-ID</strong>, asymmetric <strong>SMD-CAReh:N3</strong> and <strong>SMD-CAID</strong> exhibit larger dipole moment and fine-tuned energy. Meanwhile, more Frenkel exciton (FE)/CT states and CT mechanisms included direct excitation and hot exciton mechanisms were identified in the <strong>SMD-CAReh:N3</strong> system, which were never found in the other two systems. Moreover, the asymmetric <strong>SMD-CAReh:N3</strong> system has the highest <em>k</em>_CS, indicating favorable charge transfer. This study helps to understand the effect of asymmetric strategies on OSC performance and provide theoretical guidance for developing potential asymmetric ASM donors.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115214"},"PeriodicalIF":3.0,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143748060","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical estimations of dynamic first hyperpolarizability of D-π-A chromophores with fused (azinylmethylene)malononitrile macroacceptors","authors":"Alina I. Levitskaya ,&nbsp;Olga D. Fominykh ,&nbsp;Alexey A. Kalinin ,&nbsp;Marina Yu. Balakina","doi":"10.1016/j.comptc.2025.115203","DOIUrl":"10.1016/j.comptc.2025.115203","url":null,"abstract":"<div><div>DFT study of nonlinear-optical chromophores <strong>Q′</strong>, <strong>Q</strong>_{<strong>Ph</strong>}, <strong>PP1</strong> and <strong>Q</strong>_{<strong>on</strong>} with fused (azinylmethylene)malononitrile macro-acceptors (azine is quinoline, quinoxaline, pyridopyrazine and quinoxaline-2-one) is performed. Small effect of conformation on the first hyperpolarizability, β, values is demonstrated. The solvent effect on the molecular polarizabilities is considered by the example of dioxane and dichloromethane both for static and dynamic cases. The ratios of β(2ω) for the cases solvent/gas increase gradually in a series <strong>Q′</strong>, <strong>Q</strong>_{<strong>Ph</strong>}, <strong>PP1</strong> and <strong>Q</strong>_{<strong>on</strong>} correlating with azine moiety aromaticity decrease. The highest β(2ω), 2655⋅10⁻³⁰ esu, is obtained for <strong>Q</strong>_{<strong>on</strong>} in dichloromethane.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115203"},"PeriodicalIF":3.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical insights into the co-delivery of paclitaxel and doxorubicin on two-dimensional covalent organic frameworks","authors":"Jingping Yu ,&nbsp;Weishuo Kong ,&nbsp;Dali Wang ,&nbsp;Yingcai Fan ,&nbsp;Yang Liu","doi":"10.1016/j.comptc.2025.115216","DOIUrl":"10.1016/j.comptc.2025.115216","url":null,"abstract":"<div><div>Targeting drug delivery systems (DDS) based 2D covalent organic frameworks (COFs) have attracted more and more attention. However, there are still few reports on 2D COFs-based DDS with pH responsive release of PTX drugs. In this paper, we systematically studied the interactions between PTX molecules and COFs carrier by all-atom molecular dynamics simulations. Our results suggest that surfaces and cavities of COFs play different roles in drug delivery. For the TTI monolayer, the decrease of adsorption sites is detrimental to the adsorption of PTX molecules. Interestingly, the combined delivery of PTX and DOX can enhance the adsorption of PTX molecules on TTI monolayer and achieve pH-responsive release. For the TTI multilayer, the cavity enhanced the drugs adsorption while inhibiting the pH-responsive release of the PTX. Our study reveals the mechanism of COFs-based drug delivery system loaded with PTX drugs, which provides a promising way for applications in cancer nanomedicine.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115216"},"PeriodicalIF":3.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A theoretical study on absorbers for the intermediate band solar cell from group-IV element (Si, Ge, Sn) doped AgGaS2","authors":"Shengfengrui Zhang ,&nbsp;Changqing Lin ,&nbsp;Binyuan Huang ,&nbsp;Yang Xue ,&nbsp;Dan Huang","doi":"10.1016/j.comptc.2025.115205","DOIUrl":"10.1016/j.comptc.2025.115205","url":null,"abstract":"<div><div>Chalcopyrite compounds are employed as host materials for intermediate band solar cells owing to the wide band gaps and excellent optical properties. In this study, we focus on the chalcopyrite AgGaS₂ as a potential host for intermediate band solar cell. To identify an ideal absorber for an intermediate band solar cell, the structural stability, electronic structure, and the possibility of achieving of the large doping concentration are investigated on group-IV element (Si, Ge, Sn) doped AgGaS₂ using the first-principles calculations. Based on the <em>ab-initio</em> molecular dynamic simulation and the calculations on the phonon spectrum, the doped samples exhibited strong dynamic stabilities and thermodynamic stabilities. The calculations on electronic structures indicate that Ge and Sn doped at Ga site can form isolated and partially filled intermediate bands in AgGaS₂, whereas Si doped at Ga site cannot. In addition, the feasibility of large doping concentration is investigated, and the results show that the lowest defect formation energy is obtained for Sn doping at Ga site under Ag-poor, Ga-poor and S-rich conditions. Overall, our theoretical work suggested that Sn doped AgGaS₂ is an ideal absorber for the intermediate band solar cell.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115205"},"PeriodicalIF":3.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726217","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational study on thiolated and functionalized graphene oxide for heavy metal recovery","authors":"Corinna Lombardo,&nbsp;Giulia Varrica,&nbsp;Giuseppe Forte","doi":"10.1016/j.comptc.2025.115211","DOIUrl":"10.1016/j.comptc.2025.115211","url":null,"abstract":"<div><div>The escalating use of heavy metals in industrial, agricultural, and medical applications has amplified pollution challenges, necessitating innovative remediation strategies. This study investigates the potential of a hybrid graphene oxide/thiolated-poly(N-isopropylacrylamide) (GO/GOSH@PNM) system for the reversible, temperature-dependent removal of heavy metals, specifically Pd(II), Pb(II), and Cd(II), from aqueous environments. Molecular dynamics (MD) simulations reveal that below the lower critical solution temperature (LCST) of 32 °C, the PNM polymer adopts a hydrophilic coil configuration, enabling efficient coordination of metal cations via hydroxyl, thiol, and amide oxygen functional groups. Density functional theory (DFT) calculations corroborate these findings, highlighting favorable adsorption free energies and strong interactions between the polymer and metal ions at lower temperatures. Above 32 °C, the polymer transitions to a hydrophobic globular conformation, reducing cation affinity and facilitating their release. This temperature-induced binding and release mechanism allows for heavy metal recovery and the regeneration of the hybrid system. The GO surface demonstrates higher polymer affinity than the GOSH surface, likely due to its increased hydroxyl group density. These findings underline the potential of the GO/GOSH@PNM system for sustainable and efficient heavy metal remediation, with further optimization promising enhanced performance.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115211"},"PeriodicalIF":3.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Accelerating design of phthalocyanine-based catalysts for electrocatalytic reduction of nitric oxide: A DFT and machine learning study","authors":"Lixin Ye,&nbsp;Jiake Fan,&nbsp;Lei Yang,&nbsp;Mengyun Mei,&nbsp;Zijian Sun,&nbsp;Hui Li,&nbsp;Weihua Zhu","doi":"10.1016/j.comptc.2025.115215","DOIUrl":"10.1016/j.comptc.2025.115215","url":null,"abstract":"<div><div>Nitrogen oxide reduction reaction (NORR) is a highly efficient method for reducing NO to synthesize ammonia. Herein, we designed 18 transition-metal (TM)-doped phthalocyanine materials and combined density functional theory (DFT) with machine learning (ML) to systematically study their catalytic performance for NORR through comprehensive evaluations of their NO adsorption energy, electronic structure, and Gibbs free energy. Our results indicate that NO can adsorb on V1@Pc with a moderate adsorption energy (−2.29 eV) and the lowest limiting potential (0.38 V) among the 18 TM1@Pc materials. Additionally, V1@Pc can effectively mitigate the competitive hydrogen evolution reaction (HER), showing that it has a remarkable performance of efficiency and selectivity for NORR. Finally, machine learning techniques were employed to construct predictive models by utilizing key feature descriptors derived from DFT calculations and intrinsic atomic properties. Among the five regression models, the Random Forest Regression (RFR) exhibits the highest accuracy (R² = 0.99) and the lowest RMSE (0.15 eV) in predicting Gibbs free energy. Our study may provide valuable theoretical insights for the rational design of high-performance electrocatalysts for NORR.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115215"},"PeriodicalIF":3.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"DFT – Proposed mechanism of Friedel–Crafts acylation of indole using metal triflate catalysts","authors":"Kieu Van T. Nguyen ,&nbsp;Khung M. Trang ,&nbsp;Tam T.-V. Mai ,&nbsp;Quan Phung ,&nbsp;Phuong Hoang Tran ,&nbsp;Yoshiyuki Kawazoe ,&nbsp;Nguyen Nguyen T. Pham","doi":"10.1016/j.comptc.2025.115201","DOIUrl":"10.1016/j.comptc.2025.115201","url":null,"abstract":"<div><div>The Friedel-Crafts acylation of indole with propionic anhydride using a metal-triflate catalyst is an efficient and environmentally friendly method for synthesizing 3-acylindole, an important pharmaceutical intermediate. Despite its high selectivity for the C-3 position without requiring NH protection, the exact mechanism by which the metal-triflate catalyst promotes regioselective acylation remains unclear. In this study, density functional theory (DFT) calculations were employed to explore acyl substitution at three positions on the indole ring, both in the presence and absence of the catalyst. Two possible mechanisms were proposed: (<em>i</em>) an indirect pathway, where the catalyst forms an electrophilic intermediate (PrOTf) to acylate indole, and (<em>ii</em>) a direct pathway, where indole reacts directly with propionic anhydride at the metal core. The results indicated that the indirect pathway favored N-acylation, while the direct pathway preferred 3-acylindole. Both pathways were observed across several metal triflate catalysts (M = Y, In, Bi, La), in line with experimental data.</div></div>","PeriodicalId":284,"journal":{"name":"Computational and Theoretical Chemistry","volume":"1248 ","pages":"Article 115201"},"PeriodicalIF":3.0,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143769333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}